罗布泊“大耳朵”地区L07-11剖面沉积物重金属赋存形态研究

罗布泊“大耳朵”地区具有典型的干盐湖特征,研究该地区重金属形态分布特征,对丰富干盐湖重金属地球环境化学资料具有重要意义。首次以罗布泊“大耳朵”地区L07-11剖面沉积物中重金属Cd,Pb,Ni,Cu为研究对象,利用Tessier连续提取法对沉积物中重金属Cd,Pb,Ni,Cu的五种赋存形态进行提取,并用火焰(AAS-990)原子吸收分光光度法和石墨炉(GF-990)原子吸收分光光度法对其进行检测,并做了相关性分析。结果表明：L07-11剖面沉积物中Cd浓度的变化范围在1.10～2.54 mg·kg-1;Pb浓度的变化范围在9.18～20.02 mg·kg-1;Ni浓度的变化范围在9.88～17.15 mg·kg-1;Cu浓度的变化范围在4.43～21.11 mg·kg-1;有机质的变化范围在8.71～54.72 g·kg-1。这四种重金属的生物有效态占各重金属总含量的比例大小顺序为: Cd＞Pb＞Cu＞Ni,其中Pb和Cd主要以可交换态(包括水溶态)形式存在;Ni主要以残渣态形式存在;Cu以铁锰氧化物结合态和残渣态存在的比例较大。表层沉积物中四种重金属的有效态含量均超过了80%,除重金属Cu外,其余3种重金属可交换态含量均超过60%。重金属Cd和Pb具有较高的二次释放潜力,各重金属与沉积物中有机质之间存在一定的相关性。结果揭示了罗布泊“大耳朵”地区L07-11剖面沉积物中重金属Cd, Pb, Ni, Cu各赋存形态的分布特征,为了解该地区Cd, Pb, Ni, Cu的地球化学特征及分布状况提供了基础资料。     

污泥中重金属的形态分析及其可浸出性

以自来水厂和污水处理厂的污泥为研究对象,采用Tessier五步法和火焰原子吸收光谱法研究污泥中重金属（Zn、Cu、Cd、Ni、Mn）含量、形态分布以及可浸出性。结果发现,在自来水厂污泥和污水处理厂污泥中重金属总量大小依次为Zn〉Mn〉Ni〉Cu〉Cd,Zn〉Mn〉Cu〉Ni〉Cd,污泥中Zn含量最高,为448.17mg.kg-1;Cd含量最低,为27.17mg.kg-1,超过国家标准,限制了污泥的农用。Tessier形态分析结果表明,污泥中Zn、Cu、Cd主要以稳定态存在;Mn主要以有效态存在,潜在的迁移性和植物毒性最值得关注;Cu浸出率最高,为14.8%,Zn浸出率最低,为0.11%,因此浸出率不仅与金属和污泥的特性有关,而且金属在污泥中赋存的化学形态对其可浸出性也有重要的影响。     

温州河网沉积物中重金属分布特征与污染评价

为了调查温州河网沉积物中重金属的分布特征与污染程度,共采集了29个样,用AFS-9230原子荧光光度计和ICP-OES全谱直读电感耦合等离子发射光谱法测定样品中重金属元素含量,克里格插值图反映重金属元素的空间分布,根据内梅罗指数法建立综合地累积指数进行污染评价,利用Pearson系数法,主成分分析法进行源分析。结果表明：在不同样点重金属含量差异明显,其中Cd和Zn含量最高点为主河道城市与工业集中区,As,Pb,Hg,Cu,Ni,Cr含量最高点为机械工业园区,沉积物受到Hg,Cd,Cu,Zn,Ni和Cr污染,区域污染程度机械工业园＞主河道城市区＞三垟湿地区＞城市周边区＞水源地区,Hg,Cd,Cu,Zn,Ni和Cr具有相似的源,且以人为源为主。     

ICP-AES测定邻苯二甲酸氢钾-氢氧化钠作用下土壤中重金属全量及形态分析

空白土壤作为质量控制样品,采用邻苯二甲酸氢钾-氢氧化钠进行处理土壤样品为对照,用HNO₃-HF-HClO₄混酸对土壤样品进行消化,运用等离子体发射光谱仪(ICP-AES)测定了提取处理后土壤样品中Mo, Pb, As, Hg, Cr, Cd, Zn, Cu, Ni的全量以及酸可提取态、氧化物结合态、有机结合态三种化学形态的含量。获知不同pH的邻苯二甲酸氢钾-氢氧化钠缓冲溶液对土壤中重金属全量及形态转化作用的影响。结果表明：除Pb和Zn外,投加不同pH邻苯二甲酸氢钾-氢氧化钠缓冲溶液对土壤中重金属全量的消解和测定有促进作用。邻苯二甲酸氢钾-氢氧化钠缓冲溶液对土壤中Cr, Cu, Hg, Pb的酸可提取态、对土壤中As, Hg, Pb, Zn的氧化结合态、对土壤中As和Hg的有机结合态的转化有促进作用。在pH 5.8时,Cu和Hg的酸可提取态的含量最大值分别为2.180和0.632 mg·kg-1;在pH 6.2时,Pb的氧化结合态的含量最大值为27.792 mg·kg-1;在pH 6.0时,Hg的有机结合态含量最大值为4.715 mg·kg-1。     

利用ICP-MASS研究有机培肥土壤重金属淋溶特征

以下辽河平原11年长期定位试验为平台,采用原状土柱淋溶实验,通过比较不同用量有机肥处理土壤重金属积累情况及其淋溶特征,探讨了雨养农业条件下有机培肥措施对土壤表层重金属（Cu,Zn,Cd和Cr）积累的影响,阐述了重金属在土壤表层(0～20 cm)中的积累特征明确了重金属元素的淋溶特点和垂直迁移规律(0～60 cm)。研究表明,随着有机肥用量增加,表层土壤中Cu,Zn,Cd和Cr的含量都随之升高,积累速度为Cd＞Cu＞Zn＞Cr。根据中国土壤环境质量标准(GB15618-1995),即使施入50 t·ha-1有机肥料,也未造成表层土壤Cr, Cu和Zn的污染,其中Cr仍符合Ⅰ类土壤质量标准,而Cu和Zn符合国家Ⅱ类土壤质量标准,但对Cd而言,此时表层土壤含量已接近国家Ⅲ类土壤质量标准阈值,存在较大风险,应引起足够重视。土柱淋溶实验表明,只有个别淋溶液Cu和Cd浓度属于国家Ⅲ类水质量标准（GB/T14848—93）,其余均符合国家Ⅱ类及以上水质标准,且所有淋溶液Cr的含量都符合国家Ⅰ类水质标准,表明在下辽河平原,即使有机肥使用量达到50 t·ha-1时,仍未对地下水构成任何风险。另外,淋溶液中的重金属含量均随土层深度增加呈现下降趋势(Cr除外),表现出重金属不易下移的特点,但相对而言,Zn和Cr向深层土壤淋溶能力较强,Cu和Cd则更易积累在表层土壤。     

三峡库区万州段消落带土壤重金属形态风险评价

为了分析三峡库区消落带土壤重金属不同的化学形态危害,采集万州段8个断面的样品,通过化学连续提取法得到5种重金属Cd、Cr、Cu、Pb和Zn的5种化学形态,采用多维主成分分析方法的Tucker3模型进行评价,结果表明:在支流上游生态环境压力较大的背景下,支流和长江干流汇合区的消落带土壤重金属污染相对严重,仅Cr不超标,Cd超标最大;重金属的5种化学形态中,残渣态所占的比例最高.仅有Cd和Pb的铁锰氧化物结合态含量较高,具有较大的潜在生态风险,同时,Cd的可交换态和碳酸盐结合态含量最大,污染风险最大,是三峡库区消落带土壤中首要的污染元素.Tucker3模型可以展示采样断面、重金属种类、化学形态三个维度之间的相关性强弱,具有较好的应用前景.     

洋槐花中微量元素的光谱测定

采用火焰原子吸收法同时测定了洋槐花中K,Na,Ca,Mg,Pb,Cd,Cu,Mn,Co,Zn,Cr,Fe等1２种微量元素的含量。方法的相对标准偏差介于0.07%～2.31%, 回收率介于97.0%～107.0%。结果表明,洋槐花中含有丰富的微量元素,其含量K＞Ca＞Mg＞Na＞Fe＞Zn＞Cu＞Mn＞Co＞Pb＞Cr＞Cd, 说明洋槐花具有较高的营养价值。     

染发对头发中重金属含量的影响

化妆品和染发剂是重金属的污染源之一。应用ICP-MS对经常染发的人群头发中的重金属含量与不染发人群作了比较。结果显示,长期染发对头发中的重金属含量有明显影响,但是不同重金属变化不同。染发人群头发中重金属Mn,Fe,Ni,Cu,Cd和Sb含量明显增加,As,Cr,Zn,Ag,Pb和 Hg等重金属含量却明显减少。分析上述结果的原因可能是染发剂中含Mn,Fe,Ni,Cu,Cd和Sb偏多,含As,Cr,Zn,Ag,Pb和Hg等重金属少,而经常染发有可能影响人体对重金属As,Cr,Zn,Ag,Pb和Hg的代谢。     

北京城市污泥中铅砷镉形态浓度的ICP-MS分析

城市污泥中重金属的难降解和高毒性限制了污泥的资源化利用。以北京G和Q污水处理厂的压滤出厂污泥为实验材料,采用BCR三步浸提法对污泥中铅砷镉Pb,As,Cd的三种形态进行提取,以HNO₃-HClO₄进行全量消解,利用ICP-MS检测Pb,As,Cd的全量和各形态的含量,从而为北京城市污泥的资源开发研究提供基础数据。实验结果表明,北京城市污泥中Pb和Cd含量比上世纪末明显降低：其中,G污泥中Pb,As,Cd的全量(干重)分别为19.60,37.96和1.34 mg·kg-1,而Q污泥中分别为19.58,23.46和2.30 mg·kg-1;两种污泥中Pb含量相差甚微,G污泥中As明显高于Q污泥,而Cd则显著低于后者;两种污泥中相应金属的三种形态的变化趋势基本一致：Pb与As以HAc酸溶态为主,H₂O₂可氧化态最少;而Cd主要以NH₂OH-HCl可还原态存在,HAc酸溶态最少。三种重金属中生物毒性大的形态均占70％以上。     

ICP-AES在分析飞灰中重金属化学形态上的应用

采用ICP-AES法对垃圾焚烧飞灰中七种重金属不同化学形态的含量进行了测定。该方法快速、准确,具有较好的精密度和准确度,除个别重金属浓度接近检出限时RSD相对较大外,其余测定结果RSD＜3%,加标回收率为85.7%～100.63%。分析结果表明：飞灰中重金属Zn,Pb含量较高;Cd,Cu,Mn,Pb和Zn以碳酸盐结合态为主要形态,易进入环境;而Cr和Ni的Fe-Mn氧化物结合态最多,相对比较稳定。     

分析北京城市污泥中铅砷镉形态浓度的ICP-MS

城市污泥中重金属的难降解和高毒性限制了污泥的资源化利用.以北京G和Q污水处理厂的压滤出厂污泥为实验材料,采用BCR三步浸提法对污泥中铅砷镉Pb,As,Cd的三种形态进行提取,以HNO3-HClO4进行全量消解,利用ICP-MS检测Pb,As,Cd的全量和各形态的含量,从而为北京城市污泥的资源开发研究提供基础数据.实验结果表明,北京城市污泥中Pb和Cd含量比上世纪末明显降低:其中,G污泥中Pb,As,Cd的全量(干重)分别为19.60,37.96和1.34 mg·kg-1,而Q污泥中分别为19.58,23.46和2.30 mg·kg-1;两种污泥中Pb含量相差甚微,G污泥中As明显高于Q污泥,而Cd则显著低于后者;两种污泥中相应金属的三种形态的变化趋势基本一致:Pb与As以HAc酸溶态为主,H2O2可氧化态最少;而Cd主要以NH2OH-HCl可还原态存在,HAc酸溶态最少.三种重金属中生物毒性大的形态均占70%以上.     

Occurrence forms and leachability of inorganic species in ash residues from self-sustaining smouldering combustion of sewage sludge

This contribution reports the occurrence forms and leachability of major inorganic elements and heavy metals in the solid residue from smouldering combustion of sewage sludge (SS). Under the experimental conditions (moisture content: 50 wt%; sand-to-SS (wet) mass ratio of 4:1; and Darcy air flux: 3.5 cm/s), self-sustaining is achieved, destructing ～98% of carbon in the SS and yielding a solid ash residue rich in Si, Al, P, Fe, K and Ca. The results from BCR (European Community Bureau of Reference) sequential extraction suggest that, majority of Na, K, Al, and Fe in the smouldering residue are presented as stable residue form, while Mg and Ca exist predominantly as acid-soluble. P in the residue is contributed by both reducible and residue fractions. All the heavy metals (As, Cr, Cd, Pb, Ni and Cu) in the residue are dominated by residue form, except Zn, which exists mainly as acid-soluble and reducible forms. Leachability tests demonstrate that considerable amounts of Ca (15.23—18.82%), Mg (11.92—16.74%), and K (5.91—7.04%) are readily leached out from the smouldering residue under pH 4.2—12.0. The concentrations of all the heavy metals in leachate meet the relevant regulatory values as determined by Toxicity Characteristic Leaching Procedure (TCLP). The smouldering residue generated here has potential to recover nutrients and is safe to be disposed via landfilling, addressing the environmental concerns that hinder the further development of smouldering combustion as a SS treatment technology.     

Ultrasonic cell disruption of stabilised sludge with subsequent anaerobic digestion

The world-wide increasing environmental awareness and its subsequent regulations have led to the application of improved technologies in wastewater purification plants. This has resulted in higher wastewater and sludge productions. Sludge is the by-product of such plants and it is not only rich in organic carbon and pathogens but also in heavy metals and other environmental pollutants. In Europe, agricultural application of dried sludge (bio-solids) is confronted with negative reactions from the citizens, governmental organisations, farmers and the food industry. Ultrasonic disruption of sludge is a popular mechanical disruption process in sludge treatment. During ultrasonic treatment, high frequency acoustic signals are used to initiate the cavitation process. The applied ultrasonic field leads to a breakdown of cohesive forces of the liquid molecules resulting in the generation of cavitation bubbles. A shock wave is released by the collapse of the cavitation bubbles and propagates in the surrounding medium forming jet streams that cause the disruption of cells in sludge. Disruption of sludge cells enables the release of light organic substances into the sludge water thereby exposing them for further anaerobic digestion. This paper presents results on the disruption of conventionally stabilised sludge through the application of the ultrasonic field. In order to reduce the specific energy input (i.e. ratio of the consumed energy during ultrasonic disruption to the input sludge mass) and improve biogas production, the total solids content of the stabilised sludge was increased before disruption. The anaerobic digestion of sludge samples was carried out in a set of specially constructed laboratory anaerobic digesters. Results showed that subsequent anaerobic digestion of the ultrasonically disrupted sludge could improve biogas production with reduced sludge quantity that is vital to the economic consideration of the wastewater treatment plants. This process encourages the exploitation of valuable materials and energy from stabilised sewage sludge just before its final disposal. The negative effects of mixing disrupted sludge with its separated sludge water are also shown in this paper. This expresses the microbiological instability of the anaerobic process caused by the mixing process.     

Architecture of baked breads depicted by a magnetic resonance imaging

The architecture of baked breads made of fresh dough and frozen dough was depicted by magnetic resonance imaging (MRI). Pieces of bread (16 mm cubic cakes) were soaked in organic solvents containing various concentrations of heavy metals (Cu(2+), Co(2+) and Fe(3+)) and images of the grain structure of the breads were obtained. Of the organic solvents tested, acetone was preferable because of its single peak that prevents chemical shift effects on images, the retention of the bread structure, and the solubility of heavy metals. The heavy metals, especially Fe(3+), shortened the overly long relaxation times of acetone to practical lengths for imaging and stained the materials to provide high contrasts. The images obtained in acetone with 8 mM Fe(3+) were suitable for analyzing crumb grain structures. The bread of fresh dough showed a uniform distribution of pores of various sizes made of thin gluten sheets, whereas the pores in the bread of frozen dough were less, prominently large, non-uniformly distributed, and made of thick gluten sheets.     

Adsorption of heavy metals on sonicated activated sludge

The objective of this work is to assess heavy metals fixation capacity on sonicated activated sludge. Ultrasonic treatment of sludge has lead to its desintegration and changes physico-chemical characteristics such as soluble chemical oxygen demand, proteins or particle size distribution. This study has shown that these modifications have improved significantly the capacity of sludge to fix heavy metals. Indeed, after a sonication of 15min and storage of three days after irradiation, the equilibrium capacity is increased about 45%. The restructuration of sludge during the storage seems to increase the accessibility to active binding sites.     

Ultrasonic disintegration of biosolids for improved biodegradation

Biological cell lysis is known to be the rate-limiting step of anaerobic biosolids degradation. Shear forces generated by low frequency ultrasound can be used to disintegrate bacterial cells in sewage sludge. Thus, the quantity of dissolved organic substrate is increased. Consequently, the degradation rate and the biodegradability of organic biosolids mass are improved. Fundamental pilot-studies showed a significantly accelerated biosolids degradation with less digested sludge being produced and increased biogas production being attained. A full-scale ultrasound reactor system was developed for continuous operation under real life conditions on sewage treatment plants (STP).     

应用ICP-MS分析猪污物中铅砷镉的形态分布

为有效控制资源化过程中畜禽污物所含重金属对环境和人类健康的危害,需要监测污物中重金属的赋存形态和浓度。采集北京昌平种猪场的猪污物样品(鲜样和干清样),用BCR提取法、硝酸-高氯酸消化法和ICP-MS仪器检测铅砷镉(Pb,As,Cd)总量及各形态含量。结果表明,猪污物中Pb,As,Cd的总量分别为29.0,28.2和0.288 mg·kg-1 DW(鲜样)以及19.7,28.2 和0.134 mg·kg-1 DW(干清样),均没有超过我国的城镇垃圾农用控制标准(As接近标准值)。两类样品中重金属的形态分布规律明显不同：鲜样中三种金属可交换态及碳酸盐结合态均超过50%,有机物及硫化物结合态则低于20%;而干清样中高生态毒性的可交换态及碳酸盐结合态和Fe/Mn氧化物结合态的比例较鲜样中都明显降低(降幅可达20%以上),表明干清样用于堆肥对农田更安全。该研究结果将为北京地区养猪场污物的资源开发和生态安全评价提供重要基础数据。     

矿业废弃地重构土壤重金属含量高光谱反演

矿产资源对工业和国民经济的发展有重要的作用,但是随着矿业开采规模的扩大,资源枯竭、经营不善而形成的矿业废弃地越来越多。由于长时间受到采矿的影响,矿业废弃地土壤中存在大量的重金属元素,高浓度重金属可能会对环境和人体产生影响。土地复垦是整治污染、退化土壤再利用的重要方法,对重构后的土壤进行重金属含量检测是衡量土地复垦成效的重要指标,需要长期进行跟踪监测。传统的化学检测方法效率低、成本高、无法实现重金属大范围检测。高光谱是一种新兴的、发展潜力巨大的技术,在环境保护,资源利用,区域可持续发展等方面有着广泛的应用。经过近几十年的快速发展,仪器精度逐渐提高,检测方法逐渐成熟,为实现土壤重金属高效、便捷检测提供了可能。正常土壤重金属含量一般相对较低,采用光谱测量重金属含量较为困难,但铁矿开采区矿业废弃地由于土壤中的铁元素较多,会使土壤中的重金属的存在和聚集形式发生变化,影响重金属对光谱的响应,从而使土壤光谱反射率与重金属含量之间关系更加明显。以湖北省大冶市复垦矿区研究区,采样化学检测方法获取土壤重金属（As,Cr,Zn）含量;借助于美国ASD公司生产的FieldSpec4地物光谱仪（350～2 500 nm）获取土壤反射率,应用一阶微分、倒数对数、连续统去除法分别对反射率曲线进行预处理,提取出光谱特征波段,分析三种重金属元素与光谱特征间的相关性并建立逐步回归模型。研究表明,光谱数据预处理可使光谱特征波段更加明显,其中一阶微分和连续统去除法的效果最为明显。3种重金属元素的特征波段为495,545,675,995,1 425,1 505,1 935,2 165,2 205,2 275和2 355 nm。将土壤重金属含量与光谱特征波段之间做相关性分析,三种重金属都表现出了与光谱曲线的相关性,相关系数大部分都达到了0.5以上,最大相关系数为0.663,由于重金属种类和预处理方式的不同会导致相关性系数存在明显的差异。利用与土壤重金属相关性最大的特征波段建立三种重金属反演模型,并以反演模型r大小选择每种重金属的最优反演模型。由于重金属种类的不同,模型的选择也有差异,Cr和Zn一阶微分逐步回归为最佳反演模型,重金属As连续统去除法逐步回归为最佳反演模型。通过检验,三种重金属中Cr反演效果最好,RMSE为2.67,其次是Zn和As。对比当前不同检测手段可知,基于土样和光谱数据预处理的土壤重金属含量地物光谱仪高光谱反演是比较理想的。可为矿业废弃地土壤重金属高光谱反演提供参考。